The electron paramagnetic resonance spectra of a number of copper complexes and of vanadyl acetylacetonate were measured in solution and in the vitreous state. By a judicious choice of various mixtures of solvents, good glasses could be obtained at low temperature, which exhibited spectra with very sharp lines. In a number of cases a complete analysis of the spectrum was possible. We were then able to calculate the magnetic parameters and some properties of the wave functions by assuming either D4h or D2h symmetry. It appears that the vitreous state is well suited for a study of ligand interaction. A hyperfine splitting due to the magnetic moment of nitrogen ligand atoms could often be observed in the vitreous state when it could not be observed in the liquid state. Relaxation of ligands is qualitatively discussed.

No abstract

The first contribution t o the alkaline autoxidation of ketones was by Doering and Haines who, using t-butyl alcohol and potassium tbutoxide as solvent and base, respectively, obtained acids and aldehydes as the products. Scheme 1 was postulated t o account for the results:

The solvation of iodine in dioxan-carbon tetrachloride solutions was studied by determining a large number of absorption spectra at different compositions and different temperatures. The concentration of the iodinedioxan complex was derived from the extinction at 4515 A (at 17" C ) , the wavelength of maximal absorption of iodine in pure dioxan. as compared with the extinction of iodine in pure dioxan and in pure carbon tetrachloride, respectively. Application of the mass law resulted in equilibrium constants essentially independent of concentration. However, this was only the case when based on the assumption of a ratio of 1 : 1 for the composition of the complex. From the dependance on temperature the heat of formation of the complex was found to be 2700 cal/mol.The problem of the difference in colour of iodine solutions in Iodine solutions can be divided in two classes: different solvents is already an old one 1).

They assume interaction between the semiquinone radical-ion and quinone. As no free phenoxyradicals can be detected in phenol autoxidation, we assume that the complex between phenol and quinone exists until after the oxidation, thus rendering an interaction with another quinone molecule unlikely.